10

Factors Affecting the Stability of Crude Oil Emulsions

Petroleum Application Department Egyptian Petroleum Research Institute Egypt 1. Introduction
Crude oils are typically water in crude oil (w/o) emulsions, which are often very stable. Among the indigenous natural surfactants contained in the crude oils, asphaltenes and resins are known to play an important role in the formation and stability of w/o emulsions. Asphaltenes are defined as the fraction of the crude oil precipitating in pentane, hexane, or heptane, but soluble in toluene or benzene. Asphaltenes are the most polar and heaviest compounds in the crude oil. They are composed of several poly nuclear aromatic sheets surrounded by hydrocarbon tails, and form particles whose molar masses are included between 500 and 20,000 g mol-1. They contain many functional groups, including some acids and bases. Resins are molecules defined as being soluble in light alkanes (pentane, hexane, or heptane), but insoluble in liquid propane. They consist mainly of naphthenic aromatic hydrocarbons; generally aromatic ring systems with alicyclic chains. Resins are effective as dispersants of asphaltenes in crude oil. It was postulated that asphaltenes stabilize w/o emulsions in two steps. First, disk-like asphaltene molecules aggregate into particles or micelles, which are interfacially active. Then, these entities upon adsorbing at the w/o interface aggregate through physical interactions and form an interfacial network. The introduced chapter deals with different factors that affecting the stability of crude oil emulsions and also those factors causing asphaltenes precipitation. 1.1 Types of emulsions Emulsions have long been of great practical interest due to their widespread occurrence in everyday life. They may be found in important areas such as food, cosmetics, pulp and paper, pharmaceutical and agricultural industry (1, 2). Petroleum emulsions may not be as familiar but have a similar long-standing, widespread, and important occurrence in industry, where they are typically undesirable and can result in high pumping costs, pipeline corrosions, reduced throughput and special handling equipment. Emulsions may be encountered at all stages in the petroleum recovery and processing industry (drilling fluid, production, process plant, and transportation emulsions (3, 4). Emulsions are defined as the colloidal systems in which fine droplets of one liquid are dispersed in another liquid where the two liquids otherwise being mutually immiscible. Oil

Manar El-Sayed Abdel-Raouf

184

Crude Oil Emulsions Composition Stability and Characterization

and water produce emulsion by stirring; however, the emulsion starts to break down immediately after stirring is stopped. Depending upon the nature of the dispersed phase, the emulsions are classified as, O/W emulsion or oil droplets in water and W/O emulsion or water droplets in oil. Recently, developments of W/O/W type emulsion or water dispersed within oil droplets of O/W type emulsion and O/W/O type, Figure 1. i. Oil-in-water emulsions (O/W): The emulsion in which oil is present as the dispersed phase and water as the dispersion medium (continuous phase) is called an oil-in-water emulsion. Water-in-oil emulsion (W/O): The emulsion in which water forms the dispersed phase, and the oil acts as the dispersion medium is called a water-in-oil emulsion.

ii.

Fig. 1. Types of emulsions.

Fig. 2. (5) Schematic representation of emulsion structures. a) O/W emulsion; b) W/O emulsion. Encircled: enlarged view of a surfactant monolayer sitting at the oil-water interface.

Factors Affecting the Stability of Crude Oil Emulsions

185

1.2 Properties of emulsions (5-7) The emulsions satisfy the following criteria: Emulsions show all the characteristic properties of colloidal solution such as Brownian movement, Tyndall effect, electrophoresis etc. ii. These are coagulated by the addition of electrolytes containing polyvalent metal ions indicating the negative charge on the globules. iii. The size of the dispersed particles in emulsions in larger than those in the sols. It ranges from 1000 to 10,000 . However, the size is smaller than the particles in suspensions. iv. Emulsions can be converted into two separate liquids by heating, centrifuging, freezing etc. This process is also known as demulsification. Many advances have been made in the field of emulsions in recent years. Emulsion stability depends on presence of adsorbed structures on the interface between the two liquid phases. Emulsion behavior is largely controlled by the properties of the adsorbed layers that stabilize the oil-water surfaces (7-9). The knowledge of surface tension alone is not sufficient to understand emulsion properties, and surface rheology plays an important role in a variety of dynamic processes. When a surface active substance is added to water or oil, it spontaneously adsorbs at the surface, and decreases the surface tension (7). In the case of small surfactant molecules, a monolayer is formed, with the polar parts of the surface-active molecules in contact with water, and the hydrophobic parts in contact with oil (Fig. 2). The complexity of petroleum emulsions comes from the oil composition in terms of surface-active molecules contained in the crude, such as low molecular weight fatty acids, naphthenic acids and asphaltenes. These molecules can interact and reorganize at oil/water interfaces. These effects are very important in the case of heavy oils because this type of crude contains a large amount of asphaltenes and surface-active compounds (10-14). In petroleum industry, water-in-oil (w/o) or oil-in-water (o/w) emulsions can lead to enormous financial losses if not treated correctly. Knowing the particular system and the possible stability mechanisms is thus a necessity for proper processing and flow assurance. Thus, there are desirable or undesirable emulsions as shown in Table (1). 1.3 Emulsion formation There are three main criteria that are necessary for formation of crude oil emulsion (16): 1. 2. 3. Two immiscible liquids must be brought in contact; Surface active component must present as the emulsifying agent; Sufficient mixing or agitating effect must be provided in order to disperse one liquid into another as droplets. i.

During emulsion formation, the deformation of droplet is opposed by the pressure gradient between the external (convex) and the internal (concave) side of an interface. The pressure gradient or velocity gradient required for emulsion formation is mostly supplied by agitation. The large excess of energy required to produce emulsion of small droplets can only be supplied by very intense agitation, which needs much energy (17-21).

186

Crude Oil Emulsions Composition Stability and Characterization

Occurrence Undesirable emulsions Well-head emulsions Fuel oil emulsions (marine) Oil Sand Floatation process Oil spill mousse emulsions Tanker bilge emulsions Desirable emulsions Heavy oil pipe line emulsions Oil sand floatation process slurry Emulsion drilling fluid, oil-emulsion mud Emulsion drilling fluid, oil-base mud Asphalt emulsion Enhance oil recovery in situ emulsions Table 1. Desirable and Undesirable petroleum emulsions (10).

Usual type a W/O W/O W/O or O/W W/O O/W O/W O/W O/W W/O O/W O/W

A suitable surface active component or surfactant can be added to the system in order to reduce the agitation energy needed to produce a certain droplet size. The formation of surfactant film around the droplet facilitates the process of emulsification and a reduction in agitation energy by factor of 10 or more can be achieved. A method requiring much less mechanical energy uses phase inversion. For instance, if ultimately a W/O emulsion is desired, then an O/W emulsion is first prepared by the addition of mechanical energy. Then the oil content is progressively increased. At some volume fraction above 60-70%, the emulsion will suddenly invert and produce a W/O emulsion of smaller water droplet sizes than were the oil droplets in the original O/W emulsions (22). Emulsions of crude oil and water can be encountered at many stages during drilling, producing, transporting and processing of crude oils and in many locations such as in hydrocarbon reservoirs, well bores, surface facilities, transportation systems and refineries (23, 24). 1.4 Emulsion breakdown In general there are three coupled sub-processes that will influence the rate of breakdown processes in emulsions. These are aggregation (Flocculation), coalescence and phase separation (15), Figure 3. They will be discussed in some details.

Fig. 3. Emulsion breakdown (15).

Factors Affecting the Stability of Crude Oil Emulsions

187

Flocculation (15) It is the process in which emulsion drops aggregate, without rupture of the stabilizing layer at the interface. Flocculation of emulsions may occur under conditions when the van der Waals attractive energy exceeds the repulsive energy and can be weak or strong, depending on the strength of inter-drop forces. The driving forces for flocculation can be: 1. Body forces, such as gravity and centrifugation causing creaming or sedimentation, depending on whether the mass density of the drops is smaller or greater than that of the continuous phase. Brownian forces or Thermo-capillary migration (temperature gradients) may dominate the gravitational body force for very small droplets, less than 1 m.

2. 3.

Coalescence (15): It is an irreversible process in which two or more emulsion drops fuse together to form a single larger drop where the interface is ruptured. As already mentioned, for large drops approaching each other (no background electric field), the interfaces interact and begin to deform. A plane parallel thin film is formed, which rate of thinning may be the main factor determining the overall stability of the emulsion. The film thinning mechanism is strongly dependent on bulk properties (etc. viscosity) in addition to surface forces. The interaction of the two drops across the film leads to the appearance of an additional disjoining pressure inside the film, Figure 4. Phase separation The processes of flocculation and coalescence are followed by phase separation, i.e. emulsion breakdown.

Fig. 4. Adhesion between two emulsion droplets (10).

188 1.5 Stabilization of the emulsion

Crude Oil Emulsions Composition Stability and Characterization

There are many factors that usually favour emulsion stability such as low interfacial tension, high viscosity of the bulk phase and relatively small volumes of dispersed phase. A narrow droplet distribution of droplets with small sizes is also advantageous, since polydisperse dispersions will result in a growth of large droplets on the expense of smaller ones. The potent stabilization of the emulsion is achieved by stabilization of the interface (25- 27). 1.5.1 Steric stabilization of the interface The presence of solids at interfaces may give rise to repulsive surface forces which thermodynamically stabilize the emulsion. As concluded (28-30), many of the properties of solids in stabilizing emulsion interfaces can be attributed to the very large free energy of adsorption for particles of intermediate wettability (partially wetted by both oil and water phases). This irreversible adsorption leads to extreme stability for certain emulsions and is in contrast to the behavior of surfactant molecules which are usually in rapid dynamic equilibrium between the oil: water interface and the bulk phases. According to the asphaltene stabilization mechanism, coalescence requires the solid particles to be removed from the drop-drop contact region. Free energy considerations suggest that lateral displacement of the particles is most likely, since forcing droplets into either phase from the interface require extreme energies (31-38). The asphaltenes stabilization effect for water droplets has already been pictured in Figure 5 where droplet contact is prevented by a physical barrier around the particles.

Fig. 5. Steric stabilization of the interfaces (40). As the stability of w/o emulsions appeared clearly related to the presence of an interfacial network surrounding the water droplets (40-43), many rheological studies of water/asphalted oil interfaces have been made to clarify the mechanisms involved (44-46). The rheological properties of these interfaces have been found to be strongly dependent on the nature of solvent used for dilution, the oil concentration, the asphaltenes and resin concentrations, the resin to asphaltenes ratio, and so on (47-51).

Factors Affecting the Stability of Crude Oil Emulsions

189

1.5.2 Electric stabilization of the interface Electrical double layer repulsion or charge stabilization by polymers and surfactants with protruding molecular chains may prevent the droplets to come into contact with each other (52-54). Also, polymers, surfactants or adsorbed particles can create a mechanically strong and elastic interfacial film that act as a barrier against aggregation and coalescence. A film of closed packed particles has considerable mechanical strength, and the most stable emulsions occur when the contact angle is close to 90, so that the particles will collect at the interface. Particles, which are oil-wet, tend to stabilize w/o emulsions while those that are water-wet tend to stabilize o/w emulsions. In order to stabilize the emulsions the particles should be least one order of magnitude smaller in size than the emulsion droplets and in sufficiently high concentration. Nevertheless, stable w/o emulsions have been generally found to exhibit high interfacial viscosity and/or elasticity modulus. It has been attributed to physical cross-links between the naturally occurring surfactants in crude oil (i.e. asphaltenes particles) adsorbed at the wateroil interface (55, 56). 1.5.3 Composition of crude oil A good knowledge of petroleum emulsions is necessary for controlling and improving processes at all stages of petroleum production and processing. Many studies have been carried out in the last 40 years and have led to a better understanding of these complex systems (57-60). However there are still many unsolved questions related to the peculiar behavior of these emulsions. The complexity comes mostly from the oil composition, in particular from the surface-active molecules contained in the crude. These molecules cover a large range of chemical structures, molecular weights, and HLB (Hydrophilic-Lipophilic Balance) values; they can interact between themselves and/or reorganize at the water/oil interface. Oil-water emulsions are fine dispersions of oil in water (O/W) or of water in oil (W/O), with drop sizes usually in the micron range (61, 62). In general, emulsions are stabilized by surfactants. In some cases multiple emulsions such as water in oil in water (W/O/W) or oil in water in oil (O/W/O) can be found. Emulsions can be stabilized by other species, provided that they adsorb at the oil-water interface and prevent drop growth and phase separation into the original oil and water phases. After adsorption, the surfaces become visco-elastic and the surface layers provide stability to the emulsion (63- 65). Crude oils contain asphaltenes (high molecular weight polar components) that act as natural emulsifiers. Other crude oil components are also surface active: resins, fatty acids such as naphthenic acids, porphyrins, wax crystals, etc, but most of the time they cannot alone produce stable emulsions (65). However, they can associate to asphaltenes and affect emulsion stability. Resins solubilize asphaltenes in oil, and remove them from the interface, therefore lowering emulsion stability. Waxes co-adsorb at the interface and enhance the stability. Naphthenic and other naturally occurring fatty acids also do not seem able to stabilize emulsions alone. However, they are probably partly responsible for the important dependence of emulsion stability upon water pH. The composition of crude oil is given in Figure 6 and examples of these structures are given in Figure 7 a & b (66). These components can be separated by simple technique known as SARA analysis (Saturated, Aromatic, Resin and Asphaltenes). Some examples of the resin and asphaltenes that can be separated by using SARA analysis of are given in Figure 7a& b. The SARA analysis process is shown in Figure 8. Particles such as silica, clay, iron oxides, etc. can be

190

Crude Oil Emulsions Composition Stability and Characterization

Fig. 6. Composition of crude oil. present in crude oils. These particles are naturally hydrophilic, but can become oil-wet (hydrophobic) due to long term exposure to the crude in the absence of water. Emulsions with particles and asphaltenes combined can be much more stable than those stabilized by asphaltenes alone, provided that enough asphaltenes are present: all the adsorption sites on the particle surface need to be saturated by asphaltenes (67, 68). These species will be mentioned in some details in the next section. 1.5.4 Asphaltenes There are many definitions of asphaltenes. Strictly speaking, asphaltenes are the crude oil components that meet some procedural definition (69). A common definition is that asphaltenes are the material that is: Insoluble in n-pentane (or n-heptane) at a dilution ratio of 40 parts alkane to 1 part crude oil and (2) Re-dissolves in toluene. Chemically, asphaltenes are polycyclic molecules that are disc shaped, and have a tendency to form stacked aggregates. The tendency of asphaltenes to self-aggregate distinguishes them from other oil constituents. Asphaltene aggregation is the cause of complex non-linear effects in such phenomena as adsorption at solid surfaces, precipitation, fluids rheology, emulsion stability, etc (70, 71). Asphaltenes are regarded to be polar species, formed by condensed poly aromatic structures, containing alkyl chains, hetero atoms (such as O, S and N) and some metals. They contain also polar groups (ester, ether, carbonyl) and acidic and basic groups (carboxylic and pyridine functional groups) that can be ionized in a certain range of pH by accepting or donating protons. Typical composition of asphaltenes is provided in Table 2. Asphaltenes average molecular weights range from approximately 800 to 3000 g mol-1. They are molecularly dispersed in aromatic solvents such as toluene, and precipitate in alkanes (ASTM D2007-93, IP 143). The procedure should also specify the temperature at which the mixing and separation takes place, the amount of time that must elapse before asphaltenes are separated from the oil/alkane mixture, and even the method used to accomplish the separation (filter size,

Factors Affecting the Stability of Crude Oil Emulsions

191

Fig. 7a. Examples of molecular structures in crude oil. a- Asphaltenes, b- Resins, c- naphthenic acids. filtration rate), since all of these factors can affect the final result. Although there are several standardized procedures, but in reality every lab uses its own procedure. These may vary a little or a lot from the standards. They differ in color and in texture (72). Material separated with still lower molecular weight alkanes (e.g., propane) would be sticky and more liquid-like than those separated by n-heptane as shown in Figure 9. Some authors point out that the precipitation techniques may provide an excessively strong interference into the delicate molecular organization of asphaltenes associates (Figure 10), leading to their irreversible transformation, so that the supra-molecular architecture in solutions of the precipitated material may be different from that in native crude. Consequently, studies of aggregation in crude oil solutions may supply valuable information regarding the manner of asphaltenesasphaltenes interactions in the presence of other crude oil components. Element (in wt. %) Carbon Hydrogen Nitrogen Sulfur Oxygen Vanadium(ppm) H/C Range 78-90 6.1-10.3 0.5-3.0 1.9-10.8 0.7-6.6 0-1200 0.8-1.5 Typical 82-84 6.5-7.5 1.0-2.0 2.0-6.0 0.8-2.0 100-300 1.0-1.2

Table 2. Range and Typical Values of Elemental Composition of Asphaltenes.

192

Crude Oil Emulsions Composition Stability and Characterization

Fig. 7b. Other examples of molecular structures in crude oil.

Factors Affecting the Stability of Crude Oil Emulsions

193

Fig. 8. SARA analysis for separation of crude oil components.

n-C5 asphaltene

194

Crude Oil Emulsions Composition Stability and Characterization

n-C7 asphaltene Fig. 9. asphaltenes separated by different alkanes. Asphaltenes stabilize the crude oil emulsion by different modes of action. When asphaltenes disperse on the interface, the film formed at a water/ crude oil interface behaves as a skin whose rigidity can be shown by the formation of crinkles at interface when contracting the droplet to a smaller drop size (78). They can also aggregate with resin molecules on the interfaces and prevent droplet coalescence by steric interaction (Figure 11). Some authors suggest that asphaltenes stabilize the emulsion by formation of hydrogen bonding between asphaltenes and water molecules (79-80). Singh et al. (81) postulated that asphaltenes stabilize w/o emulsions in two steps. First, disklike asphaltenes molecules aggregate into particles or micelles, which are interfacially active. Then, these entities upon adsorbing at the w/o interface aggregate through physical interactions and form an interfacial network. Different modes of action of asphaltenes are represented in Figure 12. 1.5.5 Resins Just as the asphaltenes have only a procedural definition, resins also are procedurally defined. There are at least two approaches to defining resins. In one approach the material that precipitates with addition of propane, but not with n-heptane, is considered to constitute the resins. There is no universal agreement about the propane/n-heptane pair, but the general idea is that resins are soluble in higher molecular weight normal alkanes, but are insoluble in lower molecular weight alkanes. A standard method exists to quantify resins by a completely SARA analysis. Resins can be also defined as the most polar and aromatic species present in

Factors Affecting the Stability of Crude Oil Emulsions

195

Fig. 10. Asphaltene associates (77). deasphalted oil and, it has been suggested, contribute to the enhanced solubility of asphaltenes in crude oil by solvating the polar and aromatic portions of the Asphaltenic molecules and aggregates (82-85). The solubility of asphaltenes in crude oil is mediated largely by resin solvation and thus resins play a critical role in precipitation, and emulsion stabilization phenomena (86-88). Resins are thought to be molecular precursors of the asphaltenes. The polar heads of the resins surround the asphaltenes, while the aliphatic tails extend into the oil, Figure 13. Resins may act to stabilize the dispersion of asphaltene particles and can be converted to asphaltenes by oxidation. Unlike asphaltenes, however, resins are assumed soluble in the petroleum fluid. Pure resins are heavy liquids or sticky (amorphous) solids and are as volatile as the hydrocarbons of the same size. Petroleum fluids with high-resin content are relatively stable. Resins, although quite surface-active, have not been found to stabilize significantly water-in-oil emulsions by themselves in model systems. However, the presence of resins in solution can destabilize emulsions via asphaltenes solvation and/or replacement at the oil/water interface (89-96), Figure 13. 1.5.6 Saturates (97-100) Saturates are nonpolar and consist of normal alkanes (n-paraffins), branched alkanes (isoparaffins) and cyclo-alkanes (also known as naphthenes). Saturates are the largest single source of hydrocarbon or petroleum waxes, which are generally classified as paraffin wax,

196

Crude Oil Emulsions Composition Stability and Characterization

Fig. 11. Proposed stabilizing mechanism for asphaltenes in petroleum by resin molecules (82). microcrystalline wax, and/or petrolatum (Figure 7b). Of these, the paraffin wax is the major constituent of most solid deposits from crude oils. 1.5.7 Aromatics (101-106) Aromatics are hydrocarbons, which are chemically and physically very different from the paraffins and naphthenes. They contain one or more ring structures similar to benzene. The atoms are connected by aromatic double bonds (Figure 7b).

Factors Affecting the Stability of Crude Oil Emulsions

197

Fig. 12. Different modes of action of asphaltenes in stabilizing crude oil emulsions.

Fig. 13. Solubilization of asphaltenes by resin molecules.

198

Crude Oil Emulsions Composition Stability and Characterization

Fig. 14. Schematic illustration of asphaltene aggregates in absence and in presence of resins
(82).

2. References
[1] J. L. Grossiord, M. Seiller (1998), Multiple Emulsions: Structure, Properties and Applications. Editions de Sante, Paris. [2] P. Walstra, (1993), Principles of Emulsion Formation. Chemical Engineering Science, 48, 333-349 [3] G.W. Mushrush, J.G. Speight, Petroleum Products: Instability and Incompatibility, Taylor & Francis, Bristol, PA, 1995. [4] L.L. Schramm, Emulsions: fundamentals and applications in the petroleum Industry, Advances in Chemistry Series 231, ACS, Washington DC, 1992. [5] D. Langevin, S. Poteau, I. Hnaut and J.F. Argillier, Crude Oil Emulsion Properties and their Application to Heavy Oil Transportation, Oil & Gas Science and Technology, Rev. IFP, Vol. 59 (2004), No. 5, pp. 511-521 [6] C.W. Angle, in: J. Sjoblom (Ed.), Chapter 20. Encyclopedic handbook of emulsion Technology, Marcel Dekker, NY, 2001. [7] C.W. Angle, in: J. Sjoblom (Ed.), Chapter 24. Encyclopedic handbook of emulsion Technology, Marcel Dekker, NY, 2001. [8] D.A. Storm, S.J. DeCanio, E.Y. Sheu, in: T.F. Yen (Ed.), Asphaltene Particles in Fossil Fuel Exploration, Recovery, Refining, and Production Processes, Plenum, New York, 1994, p. 81.

Factors Affecting the Stability of Crude Oil Emulsions

199

[9] J.-R. Lin, J.-K. Park, T.F. Yen, in: T.F. Yen (Ed.), Asphaltene Particles in Fossil Fuel Exploration, Recovery, Refining, and Production Processes, Plenum, New York, 1994, p. 91. [10] R. Cimino, S. Correra, A.D. Bianco, T.P. Lockhart, in: O.C. Mullins (Ed.), Asphaltenes: Fundamentals and Applications, Plenum, New York, 1995, p. 97. [11] J. S. Buckley, Microscopic Investigation of the Onset of Asphaltene Precipitation, Fuel Sci. Tech. Internat. (1996) 14, 55-74. [12] S. Bin Othman, Study on Emulsion Stability and Chemical Demulsification Characteristics, Bachelor of Chemical Engineering, Faculty of Chemical & Natural Resources Engineering Universiti Malaysia Pahang, May 2009. [13] Mc Lean, J.D., Kilpatrick, P.K., 1997a. Effects of asphaltenes aggregation in model heptanetoluene mixtures on stability of water-in-oil emulsions. J. Colloid Interface Sci. 196, 2334. [14] Mc Lean, J.D., Kilpatrick, P.K., 1997b. Effects of asphaltenes solvency on stability of water-in-crude-oil emulsions. J. Colloid Interface Sci. 189, 242253. [15] M. Sarbar, K. M. Al-Jaziri, 1995. Laboratory investigation of factors affecting the formation and stability of tight oil-in-water emulsions in produced fluids. OAPEC Conference on New Technology 1, 261268. [16] M.E. Abdul-Raouf, A. M. Abdul-Raheim and A. A. Abdel-Azim, (2011) Surface Properties and Thermodynamic Parameters of Some Sugar- Based Ethoxylated Amine Surfactants: 1-Synthesis, Characterization, and Demulsification Efficiency, Journal of Surfactant and Detergent 14:113121. [17] J. Bibette, F. Leal-Calderon, V. Schmitt, and P. Poulin, (2002) Introduction, in: Emulsion science - Basic principles, Springer. [18] S.M. Farouq Ali, Heavy oilevermore mobile, (2003) J. Petrol. Sci. Eng. 37, 59. [19] J. S. Buckley, J. X. Wang, and J. L. Creek, (2007) "Solubility of the Least Soluble Asphaltenes," Chapter 16 in Asphaltenes, Heavy Oils and Petroleomics, eds., Springer 401-437. [20] R. Cimino, S. Correra, A. Del Bianco, and T.P Lockhart, (1995): Solubility and Phase Behavior of Asphaltenes in Hydrocarbon Media, Asphaltenes: Fundamentals and Applications, E.Y. Sheu and O.C. Mullins (eds.), NY: Plenum Press 97-130. [21] R. B. Long, (1981) The Concept of Asphaltenes, Chemistry of Asphaltenes, J.W. Bunger and N.C. Li (eds.), ACS, Washington, DC 17-27. [22] R. B.Boer, K. Leerlooyer, M. Eigner and A. van Bergen, (Feb. 1995) Screening of Crude Oils for Asphalt Precipitation: Theory, Practice, and the Selection of Inhibitors, SPE PF 10, 55-61. [23] T. Fan and J. Buckley (2002) "Rapid and Accurate SARA Analysis of Medium Gravity Crude Oils," Energy & Fuels 16, 1571-1575. [24] G. Mansoori, (1997). Modeling of asphaltene and other heavy organics depositions. J. Petrol. Sci. Eng. 17, 101111. [25] J. Murgich, (1996). Molecular recognition and molecular mechanics of micelles of some model asphaltenes and resins. Energy and Fuels 10, 6878. [26] Hirschberg, L. deJong, B. A. Schipper, and J.G.Meijer, (June 1984) Influence of Temperature and Pressure on Asphaltene Flocculation, SPEJ 24, 283-293. [27] J. Bibette, F. Leal-Calderon, V.Schmitt, V. and P. Poulin, (2002) Introduction, in: Emulsion science - Basic principles, Springer.

200

Crude Oil Emulsions Composition Stability and Characterization

[28] P. M. Spiecker, K. L. Gawrys, C. B.Trail, C.B. and P. K. Kilpatrick, (2003) Effects of Petroleum Resins on Asphaltene Aggregation and Water-in-Oil Emulsion Formation. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 220, 9-27. [29] B. P. Binks, (2002) Particles as Surfactants - Similarities and Differences. Current Opinion in Colloid & Interface Science, 7, 21-41. [30] G.A. van Aken and F. D. Zoet, (2000) Coalescence in Highly Concentrated Coarse Emulsions. Langmuir, 16, 7131-7138. [31] S. Acevedo, G. Escobar, L. B. Gutierrez, H. Rivas, and X. Gutierrez, (1993) Interfacial Rheological Studies of Extra- Heavy Crude Oils and Asphaltenes - Role of the Dispersion Effect of Resins in the Adsorption of Asphaltenes at the Interface of Water-In-Crude Oil-Emulsions. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 71, 65-71. [32] J. Sjblom, (2001) Encyclopedic Handbook of Emulsion Technology, Marcel Dekker, New York. [33] R. F. Lee, (1999) Agents which Promote and Stabilize Water-in- Oil Emulsions. Spill Science and Technology Bulletin, 5, 117-126. [34] M. Jeribi, B. Almir-Assad, D. Langevin, I. Henaut and J. Argillier, (2002) Adsorption Kinetics of Asphaltenes at Liquid Interfaces. Journal of Colloid and Interface Science, 256, 268-272. [35] W. Adamson, (1976) Physical Chemistry of Surfaces. Wiley, New York. [36] T. Tri, J. Phan, H. Harwell and A. Sabatini, (2010) Effects of Triglyceride Molecular Structure on Optimum Formulation of Surfactant-Oil-Water Systems, J Surfact Deterg, 13:189194 [37] Yeung, A., Dabros, T., Masliyah, J. and Czarnecki, J. (2000) Micropipette: a New Technique in Emulsion Research. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 174, 169-181. [38] J. D. Mclean and P. K. Kilpatrick (1997) Effects of Asphaltene Aggregation in Model Heptane-Toluene Mixtures on Stability of Water-in-Oil Emulsions. Journal of Colloid and Interface Science, 196, 23-34. [39] D. Langevin, S. Poteau, I. Henaut and F. Argillier, (2004), Crude oil emulsion properties and their application to heavy oil transportation, Oil and Gas science and technology- Rev. IFP, vol.59 No.6, pp. 652-655. [40] J. D. Mclean and P. K. Kilpatrick, (1997) Effects of Asphaltene Solvency on Stability of Water-in-Crude-Oil Emulsions. Journal of Colloid and Interface Science, 189, 242-253. [41] P. Sullivan, and P. K. Kilpatrick, (2002) The Effects of Inorganic Solid Particles on Water and Crude Oil Emulsion Stability. Industrial & Engineering Chemistry Research, 41, 3389-3404. [42] S. Arditty, C. P. Whitby, B. P. Binks, V. Schmitt and F. Leal- (2003) Some General Features of Limited Coalescence in Solid-Stabilized Emulsions. European Physical Journal, 11, 273-281. [43] N. S. Ahmed, A. M. Nassar, N. N. Zaki and K. H. Gharieb,. (1999) Stability and Rheology of Heavy Crude Oil-in-Water Emulsion Stabilized by an AnionicNonionic Surfactant Mixture. Petroleum Science and Technology, 17, 553-576. [44] K. Khristov, S. D. Taylor, J. Czarnecki and J. Masliyah, (2000), Thin Liquid Film Technique - Application to Water- Oil-Water Bitumen Emulsion Films. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 174, 183-196.

Factors Affecting the Stability of Crude Oil Emulsions

201

[45] O. V. Gafonova and H. W. Yarranton, (2001) The Stabilization of Water-inHydrocarbon Emulsions by Asphaltenes and Resins. Journal of Colloid and Interface Science, 241, 469-478. [46] Hnaut, L. Barr, J. F. Argillier, F. Brucy, and R. Bouchard, (2001) Rheological and Structural Properties of Heavy Crude Oils in Relation with their Asphaltenes Content. SPE, 65020. [47] E. Strassner, (1968) Effect of pH on Interfacial Films and Stability of Crude Oil-Water Emulsions. SPE, 1939. [48] R. Sun and C. Shook, (1996) Inversion of Heavy Crude Oil-in-Brine Emulsions. Journal of Petroleum Science and Engineering, 14, 169-182. [49] A.A.M Elgibaly, I.S. Nashawi, and M.A. Tantawy (1997) Rheological Characterization of Kuwaiti Oil-Lakes Oils and their Emulsions. SPE 37259, 493-508. [50] Sharma, V. K. Saxena, A. Kumar, H.C. Ghildiyal, A. Anurada, N. D. Sharma, B.K. Sharma and B.K. Dinesh, (1998) Pipeline Transportation of Heavy Viscous Crude oil as Water Continuous Emulsion in North Cambay Basin (India). SPE, 39537. [51] R. G. Gillies, R. Sun and C. A. Shook, (2000) Laboratory Investigation of Inversion of Heavy Oil Emulsions. Canadian Journal of Chemical Engineering, 78, 757-763. [52] T. H. Plegue, S. Frank, D. Fruman and J.L Zakin, (1986) Viscosity and Colloidal Properties of Concentrated Crude Oil in Water Emulsions. Journal of Colloid and Interface Science, 114, 88-105. [53] P. R. Garrett, (1993) Defoaming, Theory and Industrial Applications, Surfactant Science Series 45, M. Dekker, New-York. [54] J. Zhang, D. Chen, D. Yan, and X. Yang, (1991) Pipelining of Heavy Crude Oil as Oil-inWater Emulsions. SPE , 21733. [55] B.M Yaghi and A. Al Bemani, (2002) Heavy Crude Oil Viscosity Reduction for Pipeline Transportation. Energy Sources, 24, 93-102. [56] N.N. Zaki, T. Butz, and D. Kessel, (2001) Rheology, Particle Size Distribution, and Asphaltene Deposition of Viscous Asphaltic Crude Oil-in-Water Emulsions for Pipeline Transportation. Petroleum Science and Technology, 19, 425- 435. [57] N.N., Zaki, N.S. Ahmed and A.M. Nassar, (2000) Sodium Lignin Sulfonate to Stabilize Heavy Crude Oil-in-Water Emulsions for Pipeline Transportation. Petroleum Science and Technology, 18, 1175-1193. [58] T.H., Plegue, J.L., Zakin, S.G. Frank and D.H. Fruman, (1985) Studies of Water Continuous Emulsions of Heavy Crude Oils. SPE 15792. [59] I.A., Layrisse, D.R., Polanco, H., Rivas, E., Jimenez, L. Quintero, L., J. Salazar, M. Rivero, A. Cardenas, M. Chirinos, D. Rojas, D. and H. Marquez,. (1990) Viscous Hydrocarbon- in-Water Emulsions. US Patent 4 923 483. [60] N.N. Zaki, (1997) Surfactant Stabilized Crude Oil-in-Water Emulsions for Pipeline Transportation of Viscous Crude Oils. Colloids and Surfaces A-Physicochemical and Engineering Aspects, 125, 19-25. [61] G. Nunez, M. Briceno, C. Mata, H. Rivas and D. Joseph, (1996) Flow Characteristics of Concentrated Emulsions of Very Viscous Oil in Water. Journal of Rheology, 40, 405423. [62] D.H. Fruman and J. Briant, (1983) Investigation of the Rheological Characteristics of Heavy Crude Oil-in-Water Emulsions. International Conference on the Physical Modeling of Multi-Phase Flow, Coventry, England.

202

Crude Oil Emulsions Composition Stability and Characterization

[63] J.L., Salager, M.I. Briceno, and C.L. Brancho, (2001) Heavy Hydrocarbon Emulsions, In Encyclopedic Handbook of Emulsion Technology, Sjblom, J. (ed), Marcel Dekker, New York. [64] N.S., Ahmed, A.M., Nassar, N.N. Zaki and H.K. Gharieb, (1999) Formation of Fluid Heavy Oil-in-Water Emulsions for Pipeline Transportation. Fuel, 78, 593-600. [65] M.R. Khan, (1996) Rheological Properties of Heavy Oils and Heavy Oil Emulsions. Energy Sources, 18, 385-391. [66] O.V. Gafonova and H.W. Yarranton, (2001) The stabilization of water-in-hydrocarbon emulsions by asphaltenes and resins, J. Coll. Interf. Sci. 241,469478. [67] J. Sjoblom, N. Aske, I.H. Auflem, O. Brandal, T.E. Havre, O. Saether, A. Westvik, E.E. Johnsen and H. Kallevik, (2003), Our current understanding of water-in crude oil emulsions. Recent characterization techniques and high pressure performance, Adv. Col. Interf. Sci. 100102, 399473. [68] T.H Plegue, S.G Frank, D.H., Fruman and J.L. Zakin (1989) Studies of WaterContinuous Emulsions of Heavy Crude Oils Prepared by Alkali Treatment. SPE, 18516. [69] Jeribi, B. Almir-Assas, D. Langevin, I. Henaut, J.F.Argillier, Adsorption kinetics of asphaltenes at liquid interfaces, J. Coll. Interf. Sci. 256 (2002) 268272. [70] Yan, M. Gray, J. Masliyah, (2001) On water-in-oil emulsions stabilized by fine solids, Coll. Surf. A 193 97107. [71] H.W. Yarranton, H. Hussein, J. Masliyah, (2000) Water-in-hydrocarbon emulsions stabilized by asphaltenes at low concentrations, J. Coll. Interf. Sci. 228, 5263. [72] J.L. Creek, (2005). Freedom of action in the state of asphaltenes: Escape from conventional wisdom. Energy Fuels 19(4), 12121224. [73] F. Verzaro, M. Bourrel, O. Garnier, H.G., Zhou and J.F. Argillier, (2002) Heavy Acidic Oil Transportation by Emulsion in Water. SPE, 78959. [74] S. Poteau, (2004) Heavy Oil Transportation as Aqueous Emulsion. PhD Thesis Report, Paris 6 university. [75] V.A. Adewusi and A.O. Ogunsola, (1993) Optimal Formulation of Caustic Systems for Emulsion Transportation and Dehydration of Heavy Oil. Chemical Engineering Research & Design, 71, 62-68. [76] R.C. Shaw, L.L. Schramm, J. Czarnecki, Suspensions in the hot water flotation process for Canadian oil sands, in: L.L. Schramm (Ed.), Suspensions: Fundamentals and Applications in the Petroleum Industry, Advances in Chemistry Series 251, American Chemical Society, Washington, D.C., 1996, pp. 639675. [77] H. Groenzin, O.C. Mullins, (1999) Asphaltene molecular size and structure J. Phys. Chem. A 103, 1123711245. [78] L.E. Sanchez and J.L. Zakin, (1994) Transport of Viscous Crudes as Concentrated OilIn-Water Emulsions. Industrial & Engineering Chemistry Research, 33, 3256-3261. [79] R.A. Mohammed, A.I. Bailey, P.F. Luckham, S.E. Taylor, (1993) Dewatering of crude oil emulsions 1. Rheological behaviour of the crude oilwater interface, Coll. Surf. A 80: 223235. [80] T. Sun, L. Zhang, Y. Wang, S. Zhao, B. Peng, M. Li, J. Yu, (2002) Influence of demulsifiers of different structures on interfacial dilational properties of an oil water interface containing surface-active fractions from crude oil, J. Coll. Interf. Sci. 255:241247.

Factors Affecting the Stability of Crude Oil Emulsions

203

[81] S. Singh, J. D. McLean, and P. K. Kilpatrick, (1999) Fused Ring Aromatic Solvency in the Petroleum Emulsions, J. Dispersion Sci. Tech., 20, 279-293 P. [82] S. Matthew, L. Keith L. B. Gawrys, C. Trail and K. Kilpatrick, (2003) Effects of petroleum resins on asphaltene aggregation and water-in-oil emulsion formation, Colloids and Surfaces A: Physicochem. Eng. Aspects 220: 9 -27 [83] A.Yeung, T. Dabros, J. Czarnecki, J. Masliyah, (1999) On the interfacial properties of micrometre-sized water droplets in crude oil, Proc. Roy. Soc. Lond. A 455: 3709 3723. [84] G. Horvath-Szabo, J. Czarnecki, J. Malisyah, Sandwich structures at oilwater interfaces under alkaline conditions, J. Coll. Interf. Sci. 253 (2002) 427434. [85] D.E. Graham, (1988), Crude oil emulsions: their stability and resolution, in: P.H. Ogden (Ed.), Chemicals in the Oil Industry, Royal Society of Chemistry, London, pp. 155 175. [86] F.E. Bartell, D.O. Neiderhauser, (1949), Film-forming constituents of crude petroleum oils, in: Fundamental Research on Occurrence and Recovery of Petroleum, 1946 1947, American Institute of Petroleum, New York, pp. 5780. [87] C.H. Pasquarelli, D.T. Wasan, (1981), The effect of film forming materials on the dynamic interfacial properties in crude oil-aqueous systems, in: D.O. Shah (Ed.), Surface Phenomena in Enhanced Oil Recovery, Plenum Press, New York, pp. 237 248. [88] O.K. Kimbler, R.L. Reed, I.H. Silberberg, (1966) Physical characteristics of natural films formed at crude oilwater interfaces, Soc. Petr. Eng. J. 6:153165. [89] C.E. Brown, E.L. Neustadter, K.P. Whittingham, Crudeoil/water interfacial propertiesemulsion stability and immiscible displacement, Proceedings of Enhanced Oil Recovery by Displacement with Saline Solutions, May 20, 1977. London, England, pp. 91122. [90] C.G. Dodd, The rheological properties of films at crude petroleumwater interfaces, J. Phys. Chem. 64 (1960) 544550. [91] R.J.R. Cairns, D.M. Grist, E.L. Neustadter, (1976), The effect of crude oilwater interfacial properties on watercrude oil emulsion stability, in: A.L. Smith (Ed.), Theory and Practice of Emulsion Technology, Academic Press, New York, pp. 135 151 [92] H. Groenzin, O.C. Mullins, Molecular size and structure of asphaltenes from various sources, Energy Fuels 14 (2000) 677684 [93] J. G. Speight, (1999). In: J.G. Speight (ed.), Petroleum Analysis and Evaluation, Petroleum Chemistry and Refining. Taylor & Francis Press, Washington, DC. [94] R. Cimino, S. Correra, A. Del Bianco, and T.P. Lockhart (1995). In: E.Y. Sheu and O.C. Mullins (eds.), Asphaltenes: Fundamentals and Applications. Plenum Press, New York, p. 126. [95] L. S. Kotlyar, B.D. Sparks, and J.R. Woods (1999). Solids associated with asphaltenes fraction of oil sands bitumen. Energy & Fuel 13, 346350. [96] E. Y. Sheu, (1998). In: O.C. Mullins and E.Y. Sheu (eds.), Structure and Dynamics of Asphaltenes and other petroleum fractions, Plenum Press, New York. p.115. [97] B. T. Ellison, C.T. Gallagher, L.M. Frostman, and S.E. Lorimer (2000). The physical chemistry of wax, hydrates and asphaltene. In: Offshore Technology Conference, Houston, TX, May 14, 2000, OTC 11963.

204

Crude Oil Emulsions Composition Stability and Characterization

[98] W. A. Gruse and D.R. Stevens (1960). The Chemical Technology of Petroleum. McGraw-Hill, New York. [99] R. G. Draper, E. Kowalchuk, and G. Noel (1977). Analyses and characteristics of crude oil samples performed between 1969 and 1976. Report EPR/ERL 77-59, Energy, Mines, and Resources, Canada. [100] J. G. Speight, (1991). The Chemistry and Technology of Petroleum, 2nd edn. Marcel Dekkar Inc., New York. [101] W.D. McCain, Jr. (1990). The Properties of Petroleum Fluids, 2nd edn. PennWell Publishing Co., Oklahoma. [102] W. A. Cruse and D.R. Stevens (1960). In: Chemical Technology of Petroleum. McGrawHill Book Publishers Inc., New York City, Chap. XXII. [103] C. Lira-Galeana and A. Hammami (2000). In: T.F. Yen and G. Chilingarian (eds.), Asphaltenes and Asphalts. Elsevier Science Publishers, Amsterdam. Chap. 21. [104] H. Warth, (1956). In: The Chemistry and Technology of Waxes, 2nd edn. Reinhold, New York. [105] O.P. Starusz,, T.W. Mojelski, and E.M. Lown (1992). Fuel 71, 13551364. [106] D. Espinat, (1993). In: SPE International Symposium on Oilfield Chemistry, New Orleans, LA, March 25, 1993, SPE 25187.